EXCHANGE 


ANTHRAQUINONE:!,    8    ALIPHATIC   THIO- 

ETHER-SULPHONIC   ACIDS  AND 

DI-THIO-ETHERS. 


A  DISSERTATION 

SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF 

THE  JOHNS  HOPKINS  UNIVERSITY  IN  CONFORMITY 

WITH  THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY. 


BY 

GEORGE  EDGAR  MILLER 


June  1920, 


ANTHRAQUINONE:!,    8    ALIPHATIC    THIO- 

ETHER-SULPHONIC   ACIDS   AND 

DI-THIO-ETHERS. 


A  DISSERTATION 

SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF 

THE  JOHNS  HOPKINS  UNIVERSITY  IN  .CONFORMITY 

WITH  THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY. 


BY 

GEORGE  EDGAR  MILLER 


June  1920. 


CONTENTS. 

Acknowledgment   ." 4 

Introduction   5 

Historical    6 

Properties 8 

Experimental   9 

Procedure   9 

Plan  12 

Anthraquinone-l-Thio-Ether-8-Sulf  onic  Acids 13 

Biography . .  29 


461991 


ACKNOWLEDGMENT. 

The  work  described  in  the  following  pages  was  car- 
ried out  at  the  suggestion  and  under  the  supervision  of 
Dr.  E.  Emmet  Reid.  The  writer  wishes  to  take  this  op- 
portunity to  thank  him  for  his  help  and  interest  in  this 
work.  He  also  wishes  to  thank  Drs.  Remsen,  Frazer, 
Patrick,  Lovelace,  Lloyd  and  Swartz  for  instruction  re- 
ceived from  them  during  his  course  as  a  student  at  Johns 
Hopkins  University. 

The  writer  also  feels  under  obligations  to  Drs.  Thorn- 
ton, and  Millikan  for  helpful  suggestions  which  they 
made. 


ANTHRAQU1NONE:!,    8    ALIPHATIC    THIO- 

ETHER-SULFONIC  ACIDS  AND 

DI-THIO-ETHERS. 


INTRODUCTION. 

In  the  hope  of  obtaining  derivatives  of  anthraquinone- 
sulfonic  acids  which  would  have  suitable  melting  points 
for  their  identification,  the  problem  of  replacing  sulfonic 
acid  groups  was  undertaken.  It  was  known  that  sulfonic 
acid  groups  of  anthraquinone-sulphonic-acids  could  be 
replaced  by  methoxy1  or  phenoxy  groups2  and  that  the 
resulting  compounds,  C14H702.OCH3  and  C14H702.  OC6 
H5  are  crystalline  and  have  definite  though  rather  high 
melting  points. 

Hence  it  was  thought  that  a  compound  of  the  formula 
C14H702.  S  R  would  be  of  service.  Normal  butyl  mercap- 
tan  was  used  as  being  readily  available,  and  it  was 
thought  probable  that  the  compound  would  have  a  low 
melting  point,  since  sulfur  compounds  usually  melt  lower 
than  the  corresponding  oxygen  compounds  and  since 
butyl  derivatives  are  apt  to  melt  considerably  lower  than 
methyl  and  much  lower  than  phenyl  derivatives.  The 
desired  reaction  was  found  to  take  place  readily, 
although  not  quantitatively  when  the  sulfonic  acid  group 
is  in  the  alpha  position  and  the  resulting  compounds 
were  found  to  have  convenient  melting  points  suitable 
for  the  identification  of  anthraquinone  alpha  sulphonic 
acid  and  anthraquinone  1,5  and  1,8  disulphonic  acids. 

The  ease  with  which  the  reaction  takes  place  and  the 
interesting  character  of  the  compounds  obtained  led  to 
a  study  of  derivatives  of  other  mercaptons  in  combina- 
tion with  1,8  disulfonic  acid. 

1  D.  R.  P.  156762. 

2  D.  R.  P.  158531. 


HISTORICAL. 

Anthraquinone  aliphatic  thio-ether-sulfonic  acids  and 
di  thio-ethers  may  be  prepared  by  the  action  of  aliphatic 
mercaptans  on  anthraquinone  sulfonic  acids  in  alkaline 
solution.3  In  this  way  Bayer  and  Company  prepared 
anthraquinone  1,  ethyl-thio-ether,  5  sodium-sulphonate 
and  1,5  di-ethyl-thio-ether. 

Gattermann4  has  shown  that  the  nitro  group  in  nitro 
anthraquinone  is  replaced  by  the  alkoxy  group  when 
treated  with  sodium  alcoholate,  thus: 


A.  N02+NaOC2H5-*A.  OC2H5+Na  N02 


Representing  the  anthraquinone  residue  by  A.  He  at- 
tempted to  carry  out  the  analogous  reaction  using  alka- 
line mercaptan  in  order  to  abtain  anthraquinone-thio- 
ether.  This  reaction,  however,  resulted  in  the  reduction 
of  the  nitro  group  to  the  amino  group.  On  the  other 
hand  he  found  that  treatment  with  alkaline  aromatic 
mercaptans  readily  caused  a  quantitative  replacement  of 
the  nitro  group  with  the  formation  of  aromatic  thio- 
ethers. 


A.  N02+NaSC6H5^A.SC6H5+Na  NO, 


Gattermann5    has    also    prepared    anthraquinone   ali- 


3  D.  R.  P.  224589- 

4  D.  R.  P.  75054.    . 

5  Loc.  cit-,  and  Liebig*s  Annalen,  303,  138-139,  179-180  (1912). 


phatic  thio-ethers  and  thio-ether-sulfonic-acids  indirect- 
ly by  diazotizing  amino-anthraquinones  or  amino  an- 
thraquinone-sulfonic  acids  in  concentrated  sulfuric  acid. 
Subsequent  treatment  of  the  diazo  compound  with  potas- 
sium thio  cyanate  yielded  anthraquinone  thio  cyanate 
which  on  boiling  with  alcoholic  potash  gave  the  thio- 
ether  or  thio  ethersulfonic-acid.  In  this  way  he  prepar- 
ed anthraquinone  alpha  ethyl-thio-ether ;  anthraquinone 
methyl-thio-ether  5  potassium  sulfonate;  and  anthra- 
quinone methyl-thio-ether  8  potassium  sulfonate,  thus : 


A.N02-»A.NH2-»A.SCN 
A.SCN+KOCH3^A.SCH3+KOCN 


In  the  present  investigation  it  is  shown  that  anthra- 
quinone 1,8  di  sodium  sulfonate  when  heated  with  ali- 
phatic mercaptans  in  alkaline  solutions  react  readily  to 
form  thio-ether-sulfonic-acids  and  di-thio-ethers,  the  sul- 
fonic  acid  groups  being  replaced  in  turn  according  to 
the  following  reactions: — 


-h  Na^SO, 


SCHi 


+  NaSCH5  n 


PROPERTIES. 

The  anthraquinone  thio-ether-sodium-sulfonates  are 
soluable  in  water,  the  derivatives  of  the  lower  mercap- 
tans  being  more  soluble  than  those  of  the  higher  mercap- 
tans.  They  crystallize  from  water  in  orange  to  orange 
red  needles  containing  one  molecule  of  water  of  hydra- 
tion  with  the  exception  of  the  propyl  derivative  which 
contains  one-half  molecule  of  water.  Other  salts  of 
these  acids  are  highly  colored  ranging  from  light  yellow 
through  shades  of  orange  to  red,  and  are  in  general  well 
crystallized. 

Anthraquinone  di-thio  ethers  are  insoluable  in  water, 
slightly  soluble  in  alcohol  and  very  soluble  in  benzene. 
In  this  case  the  derivatives  of  the  higher  mercaptans  are 
markedly  more  soluble  than  those  of  the  lower  members 
of  the  series.  When  crystallized  from  benzene  they  form 
lustorus  crystals  varying  in  color  from  light  yellow  to 
deep  orange  red. 


9 


EXPERIMENTAL. 

MATERIALS. 

The  anthraquinone  1,8  di-sodium-sulfonate  was  ob- 
tained through  the  courtesy  of  E.  I.  du  Pont  de  Nemours 
&  Company. 

The  methyl  mercaptan  was  generated  by  dropping  di- 
methyl sulfate  into  warm  sodium  hydrosulfide,  which 
was  prepared  by  warming  Na2S  .  9H2O  to  about  90 °C, 
and  saturating  with  hydrogen  sulfide. 

The  ethyl  mercaptan  was  prepared  in  a  similar  man- 
ner using  sodium  ethyl  sulfate. 

The  propyl,  butyl  and  iso  amyl  mercaptans  were  pre- 
pared by  the  catalytic  method  of  Kramer  and  Reid.6 

PROCEDURE. 

I.  Preparation  of  anthraquinone-thio-ether-sulfonic- 
acids. 

Anthraquinone  1,8  di-sodium-sulfonate  was  suspended 
in  boiling  water  containing  about  two  equivalents  of 
caustic  soda.  In  the  case  of  the  more  volatile  mercap- 
tans, methyl  and  ethyl,  the  mercaptans  were  generated 
in  another  flask,  as  previously  described  and  passed,  in 
vapor  form,  into  the  alkaline  reaction  mixture  which 
was  gently  boiled  and  vigorously  stirred.  The  less  vola- 
tile mercaptans  were  weighed  into  the  alkaline  mixture 
and  boiled  under  reflux.  Slightly  more  than  enough  mer- 
captan to  replace  one  sulfonic  acid  group  was  used. 
Since  all  the  1,8  thio-ether-sulfonic-acids  are  compara- 
tively soluble  the  formation  of  di-thio-ether  is  favored, 
so  that  the  reaction  must  be  stopped  at  the  proper  time 
in  order  to  get  a  minimum  amount  of  the  di-thio-ether. 
This  was  separated  from  the  dried  thio-ether-sulfonic 
acid  by  extraction  with  boiling  benzene  after  which  the 
salt  was  recrystallized  from  water. 

II.  Preparation  of  anthraquinone  di-thio-ether s. 
When  the  di-thio-ethers  were  desired  more  mercaptan 

6    Private  communication. 


10 

was  used  and  the  heating  continued  until  the  second  sul- 
fonic  acid  group  was  replaced. 

The  mixed  di-thio-ethers  were  obtained  by  gently  boil- 
ing an  alkaline  suspension  of  the  purified  anthraquinone 
thio-ether-sodium  sulfonate  with  a  different  mercaptan. 
Owing  to  the  greater  solubility  of  the  thio-ether-sodium- 
sulfonates  derived  from  the  relatively  lower  mercaptans 
it  was  found  preferable  to  employ  the  mercaptan  of 
higher  molecular  weight  last. 

The  separation  of  yellow  or  reddish  yellow  needles  in- 
dicated the  course  of  the  reaction.  The  product  was  fil- 
tered, washed  with  hot  water  until  the  filtrate  was  color- 
less, dried  and  re-crystallized  from  benzene. 

III.  Preparation  of  Sulfones. 

The  sulfones  were  prepared  by  oxidizing  the  anthra- 
quinone di-thio-ethers  with  fuming  nitric  acid.  The  re- 
action product  was  poured  into  hot  water,  filtered  and 
washed. 

IV.  Preparation  of  Salts. 

The  metallic  and  organic  salts  of  the  above  acids  were 
prepared  by  adding  a  solution  of  nitrate,  chloride  or 
sulf ate  of  the  desired  base  to  a  hot  solution  of  an  equiva- 
lent amount  of  the  anthraquinone-thio-ether-sodium-sul- 
fonate.  The  less  soluble  salt  separating  out.  The  nearly 
insoluble  salts  were  purified  by  boiling  with  water. 

V.  Analytical 

1.  Sulfur. 

Sulfur  was  determined  by  means  of  the  Parr  bomb, 
using  O.  2  gram  samples  and  5.  0  grams  of  sodium 
peroxide,  with  subsequent  precipitation  of  barium  sul- 
fate. 

2.  Water  of  Hydration. 

l.O  gram  samples  were  exposed  to  an  atmosphere  of 
50%  humidity  for  48  hours,  then  heated  to  constant 
weight  in  a  vacuum  at  110°C.  2  to  4  hours  being  generally 


11 

sufficient  to  remove  all  the  water.  A  dead  air  humidor 
containing  44%  sulfur  acid  was  used  to  obtain  the  50% 
humidity.  A  modified  and  enlarged  Abdenhalden  vapor- 
vacuum  oven,  capable  of  holding  four  100mm  combus- 
tion boats  was  designed  and  constructed  according  to  the 
following  plan. 

3.  Sodium,  Barium,  Strontium,  Calcium,  Nickel  and 
Cobalt. 

0.5  gram  samples,  dried  as  above,  were  ignited  in  a 
platinum  crucible  until  the  carbon  was  burned  off  as 
completely  as  possible.  The  residue  was  then  evaporated 
with  concentrated  sulfuric  acid,  and  re-ignited  with 
ammonium  carbonate  to  constant  weight.  The  metal 
was  weighed  as  the  sulfate. 

4.  Lead. 

O.5  gram  samples  were  ignited  cautiously,  and  evapor- 
ated with  nitric  acid  to  dissolve  any  reduced  lead.  The 
residue  was  evaporated  with  concentrated  sulfuric  acid 
and  re-ignited  with  ammonium  carbonate  to  constant 
weight.  The  metal  was  weighed  as  the  sulfate. 

5.  Copper. 

The  copper  was  precipitated  in  a  faintly  ammoniacal 
solution  with  hydrogen  sulfide.  The  precipitate  was  fil- 
tered, dried,  ignited  and  weighed  as  cupric  oxide.  Inas- 
much as  the  percentage  of  copper  is  the  same  in  cupric 
oxide  and  cuprous  sulfide  the  combustion  was  not  com- 
plete. 


13 


ANTHRAQUINONE-1-THIO-ETHER-8SUL- 
FONIC  ACIDS. 

Anthraquinone-1 -Methyl   Thio-Ether-8-Sodium-Sulfonate 

1-CH3S.C6H3  (CO)  2  C6H3-8-S03Na.H20 

Methyl  mercaptan  was  passed  for  two  hours  into  a 
suspension  of  82  grams  of  anthraquinone  1-8  di-sodium- 
sulfonate  in  25  grams  of  sodium  hydroxide  and  500  cc. 
water.  Yield  57  grams  of  a  brick  red  crystalline  powder 
which  does  not  melt  at  300°  C. 

Substance  1.0061  g.  lost  0.0487  g. 

Calculated  for  C15H905S2Na.  H20  :  H20  4.81%  found 
4.84%. 

Substance  anhydrous  0.5006  gave  0.1021  g.  Na2S04. 

Calculated  for  C15H905S2Na  :  Na  6.45%  found  6.60%. 


Anthraquinone-l-Methyl-Thio-Ether-8-Barium    Sulfonatc. 

1-CH3S.C6H3(CO)2  C6H3-8-SO3i/2  Ba. 

Crystallizes   from   water   in   dark   brick   red   needles 
which  do  not  melt  at  300°C. 

Substance  0.5003  g.  gave  0.1422  g.  BaS04. 
Calculated  for   (C15H905S2)2  Ba:Ba.       17.09%  found 
16.73%. 


Aniline    Salt    of    Anthraquinone-1-Methyl     Thio-Ether-8-SuIfonic 

Acid. 

1-CH3S.C6H3.  (CO)  2.C6H3-8-S03HNH2C6H5. 

Crystallizes  in  orange  needles   which  melt  at  about 
260°  with  decomposition. 

Substance  0.2000  g.  gave  0.2161  g.  BaS04. 
Calculated  for  C21H17O5S2N:S2.  15.00%  found  14.85%. 


14 


Ortho    Toluidine    Salt    of    Anthraquinone-l-Methyl-Thio-Ether-8- 

Sulfonic  Acid. 

1-CH3S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H4CH3. 

Yellow  needles  which  m.elt  at  about  255 °C  with  de- 
composition. 

Substance  0.2007  g.  gave  0.2087  g.  BaS04. 
Calculated  for  C22H1905S2N:S2.    14.53%  found  14.30%. 


Para     Toluidine     Salt     of     Ant  hraquinone-1- Methyl -Thio-Ether-8* 

Sulfonic  Acid. 

1-CH3S.   C6H3.  (CO)  2.C6H3-8-S03H.NH.2C6H4CH3. 

Orange  needles  which  melt  at  about  260°  with  decom- 
position. 

Substance  0.2011  g.  gave  0.2107  g.  BaS04. 
Calculated  for  C22H1805S2N:S2.  14.53%  found  14.37%. 


Anthraquinone-l-EthyI-Thio-Ether-8-Sodium    Sulfonate. 

1-C2H5S.C6H3  (CO)  2C6H3-8-S03Na. 

Gaseous  ethyl  mercaptan  was  passed  into  82  grams  of 
anthraquinone  1-8  di-sodium  sulfonate  suspended  in  500 
cc.  of  water  and  25  grams  of  sodium  hydroxide  for  3 
hours.  Yield  45  grams  of  orange  red  needles  which  do 
not  melt  at  300 °C. 

Substance  0.3031  g.  gave  0.0571  g.  Na2S04. 

Calculated  for  C^H^O^NaiNa  6.21%  found  6.11%. 


Ant  hraquinone-l -Ethyl -Thio-Ether-8- Barium    Sulfonate. 

1-C2H5S.  C6H3  (CO)  2C6H3-8-S03i/2Ba. 

Orange  red  needles  which  do  not  melt  at  300°C. 
Substance  0.3009  g.  gave  0.0834  g.  BaS04. 
Calculated    for     (C16H11O5S2)2Ba:Ba.    16.51%    found 
16.31%. 


15 

Anthraquinonc-l-Propyl-Thio-Ether-8-Sodium  Sulfonate. 

1-C3H7S.C6H3  (CO)  2C6H3-8-S03Nai/2H20. 

82  grams  of  anthraquinone  1-8  di-sodium  sulfonate, 
suspended  in  500  cc.  water  and  8  grams  sodium  hydro- 
xide were  refluxed  with  40  grams  of  80%  propyl  mer- 
captan  for  three  hours.  Yield  21  grams  of  ochre  yellow 
crystalline  powder  which  melts  at  289 °C. 

Substance  1.0063  g.  lost  0.0228  g. 

Calculated  for  C17H1305S2Nay2H20:i/2H20.  2.29% 
found  2.26%. 

Substance  0.5025  g.  gave  0.0967  g.  Na2S04. 

Calculated  for  C17H1305S2Na:Na.  5.98%  found  6.23%. 

Anthraquinon«-l-Propyl-Thio-Ether-8-Barium    Sulfonate. 

1-C3H7S.C6H3  (CO)  2C6H3-8-S03i/2Ba. 

Orange  powder  does  not  melt  at  300° C. 
Substance  0.3003  g.  gave  0.0821  g.  BaS04. 
Calculated    for     (C17H1305S2)2Ba:Ba.    15.97%    found 
16.08%. 

Aniline      Salt      of     Anthraquinone- l-Propyl-Thio-Ether-8-Sulfonic 

Acid. 

1-C.HTS.C.H,  (CO)  2C6H3-8-S03H.NH2.C6H5. 

Orange  needles  which  melt  at  about  250°  with  decom- 
position. 

Substance  0.2012  g.  gave  0.2054  g.  BaS04. 
Calculated  for  C23H2105S2N:S2.  14.08%  found  14.01%. 

Ortho     Toluidine     Salt     of     Anthraquinone-1-Propyl-Thio-Ether-S- 

Sulfonic  Acid. 

1-C3H7S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H4CH3. 

Yellow  needles  which  melt  about  260 °C  with  decom- 
position. 

Substance  0.2016  g.  gave  0.2003  g.  BaS04. 

Calculated  for  C24H2305S2N:S2.    13.66%  found  13.64%. 


16 

Para     Toluidine     Salt     of     Anthraquinone- l-Propyl-Thio-Ether-8- 

Sulfonic  Acid. 

1-C3H7S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H4CH3. 

Orange  yellow  needles  which  melt  at  about  255  °C  with 
decomposition. 

Substance  0.2006  g.  gave  0.1983  g.  BaS04. 
Calculated  for  C24H2305S2N  :S2.  13.66%  found  13.56%. 

Anthraquinone-l-Butyl-Thio-Ether-8-Sodium    Sulfonate. 

1-C4H9S.  C6H3  (CO)  2C6H3-8-S03Na.H20. 

82  grams  of  anthraquinone  1-8  di-sodium  sulfonate 
suspended  in  500  cc.  of  water  and  8  grams  of  sodium 
hydroxide  were  refluxed  with  30  grams  of  butyl  mercap- 
tan  for  two  hours.  Yield  30  grams  of  orange  yellow 
needles  which  do  not  melt  at  300°C. 

Substance  3.2320  g.  lost  0.1420  g. 

Calculated  for  C18H1505S2Na.  H20:H20.  4.33%  found 
4.39%. 

Substance  0.5046  g.  gave  0.0872  g.  Na2S04. 

Calculated  for  C18H1505S2Na  :Na  5.77%  found  5.59%. 

Anthraquinone- 1 -Butyl -Thio-Ether-8- Barium    Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Ba.    ' 

Fine  orange  yellow  needles  which  do  not  melt  at 
300°C. 

Substance  0.5008  g.  gave  0.1285  g.  BaS04. 
Calculated    for    (C18H1505SJ2Ba:Ba.     15.47%    found 
15.12%. 

Anthraquinone- 1- Butyl -Thio-Ether-8- Strontium   Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Sr. 

Orange  red  crystalline  powder  which  does  not  melt  at 
300°  C. 

Substance  0.5007  g.  gave  0.1116  g.  Sr.S04. 
Calculated   for    (C18H1505S2)2    Sr:Sr.    10.45%    found 
10.63%. 


17 

Anthraquinone-l-Butyl-Thio-Ether-8-CaIcium    Suifonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Ca.4  H20. 

Red  crystalline  powder  which  does  not  melt  at  300°C. 

Substance  1.0006  g.  lost  0.0788  g. 

Calculated  for  C18H1505S2i/2Ca.4  H20:4   H20.   8.35% 

found  7.87%. 

Substance  0.5021  g.  gave  0.0871  g.  CaS04. 
Calculated    for    (C18H1505S2)2    Ca:Ca.    5.07%    found 

5.10%. 


Anthraquinone-l-Butyl-Thio-Ether-8-Lead  Sulfonate 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Pb. 

Orange  red  powder  which  does  not  melt  at  300 °C. 
Substance  0.5008  g.  gave  0.1590  g.  PbS04. 
Calculated   for    (C18H1505S2)2   Pb:Pb.   21.63%    found 
21.69%. 


Anthraquinone-l-Butyl-Thio-Ether-8-Nickel   Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Ni.XH20. 

Orange  red  needles  which  do  not  melt  at  300° C.    The 
water  of  hydration  is  undetermined. 

Substance  0.5025  g.  gave  0.0938  g.  NiS04. 
Calculated    for     (C18Hl505S2)2Ni:Ni.     7.25%     found 
7.08%. 


Anthraquinon»-l-Butyl-Thio-Ether-8-Cobalt    Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Co.XH20. 

Orange  red  needles  which  do  not  melt  at  300 °C.    The 
water  of  hydration  is  undetermined. 

Substance  0.5061  g.  gave  0.0985  g.  CoS04. 
Calculated    for    (C18H1505S2)2    CorCo.    7.28%    found 
7.40%. 


18 

Anthraquinone-l-Butyl-Thio-Ether-8-Copper   Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Cu.li/2H20. 

Ochre  yellow  powder  which  does  not  melt  at  300  °C. 

Substance  1.0040  g.  lost  0.0342  g. 

Calculated  for  C18H1505S2i/2Cu.li/2H20:li/2H20.  3.21% 

found  3.40%. 

Substance  0.2000  g.  gave  0.0196  g.  CuO. 
Calculated    for    (C18H15O5S2)2    Cu:Cu.     7.81%    found 

7.85%.  :    '  I    i  !  f ; 


Aniline       Salt      of      Anthraquinone-l-ButyI-Thio-Ether-8-Sulfonic 

Acid. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H3. 

Yellow  needles  which  melt  at  about  242  °C  with  de- 
composition. 

Substance  0.2000  g.  gave  0.2014  g.  BaS04. 

Calculated  for  C24H2305S2N  :S2.  13.66%  found  13.85%. 


Ortho     Toluidine     Salt     of     Anthraquinone-l-Butyl-Thio-Ethcr-8- 

Sulfonic  Acid. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H4CH3. 

Yellow  needles  which  melt  at  about  260 °C  with  de- 
composition. 

Substance  0.2000  g.  gave  0.1979  g.  BaS04. 

Calculated  for  C25H2505S2N:S2.  13.26%  found  13.60%. 

Para     Toluidine     Salt      of     Anthraquinone-l-Butyl-Thio-Ether-8- 

Sulfonic  Acid. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03H.NH2C6H4CH3. 

Yellow  needles  which  melt  at  about  260° C  with  de- 
composition. 

Substance  0.2000  g.  gave  0.1965  g.  BaS04. 
Calculated  for  C25H2505S*N:S2.  13.26%  found  13.50%. 


19 

Anthraquinone-l -Butyl -Thio-Ether-8- Silver    Sulfonate. 

1-C4H9S.  C6H3  (CO)2C6H3-8-SO3Ag.XH20. 
Canary  yellow  needles. 

• 

Anthraquinone-l-ButyI-Thio-Ether-8-Cadmium    Sulfonate. 

1-C4H9S.  C6H3  (CO)2C6H3-8-S03i/2Cd.XH20. 
Orange  needles. 

Anthraquinone-l-ButyI-Thio-Ether-8- Mercuric  Sulfonate. 

1-C4H9S.  C6H3  (CO)2C6H3-8-S03i/2Hg.XH20. 
Orange  needles. 

Anthraquinone-l -Butyl-Thio-Ether-8-Mangane»e   Sulfonate. 

1-C4H9S.C6H3  (CO)2C6H3-8-S03i/2Mn  XH20. 
Red  needles. 

Anthraquinone-l-ButyI-Thio-Ether-8-Zinc   Sulfonate. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S03i/2Zn  XH20. 
Orange  red  needles. 

Anthraquinone-l -Butyl -Thio-Ether-8- Aluminium   Sulfonate. 

1-C4H9S.C6H3  (CO) 2C6H3-8-S03V3Al  XH20. 
Orange  red  needles. 


20 

Anthraquinonc-l-I»o-AmyI-Thio-Ether-8-Sodium   Sulfonate. 

l-C^S.CeH,  (CO)  2C6H3-8-S03Na.H20. 

82  grams  of  anthraquinone  1-8  di-sodium  sulfonate 
suspended  in  500  cc.  water  and  10  grams  sodium  hy- 
droxide were  refluxed  with  32  grams  of  80%  iso-amyl 
mercaptan  for  four  hours.  Yield  50  grams  of  brownish 
orange  needles  which  do  not  melt  at  300°C. 

Substance  1.0039  g.  lost  0.0418  g. 

Calculated  for  C19H1705S2Na.H20  :H20.  4.19|%  found 
4.16%. 

Substance  0.5011  g.  gave  0.0841  g.  Na2S04. 

Calculated  for  C19H1705S2Na  :Na.  5.58%  found  5.34%. 

Anthraquinone-l-Iso-AmyI-Thio-Ether-8-Barium    Sulfonate. 

l-C.H^S.  C6H3  (CO)  2C6H3-8-S03i/2Ba. 

Orange  yellow  needles  which  do  not  melt  at  300°C. 
Substance  0.5021  g.  gave  0.1262  g.  BaS04. 
Calculated  for    (C19H1705S2)2   Ba:Ba.    14.99%    found 
14.80%. 


Aniline   Salt    of   Anthraquinone-l-Iso-Amyl-Thio-Ether-8-Sulfonic 

Acid. 

l-C5HnS.  C6H3  (CO) 2C6H3-8-S03HNH2C6H5. 

Orange  needles  which  melt  at  about  260  °C  with  decom- 
position. 

Substance  0.2004  g.  gave  0.1966  g.  BaS04. 

Calculated  for  C25H2505S2N  :S2.  13.26%  found  13.47%. 


Ortho  Toluidine  Salt  of  Anthraquinone-l-Iso-Amyl-Thio-Ether-8- 

Sulfonic  Acid. 

l-C^^S.CeH,  (CO)  2C6H3-8-S03HNH2C6H4CH3. 

Orange  needles  which  melt  at  about  260  °C  with  de- 
composition. 

Substance  0.2005  g.  gave  0.1911  g.  BaSO4. 
Calculated  for  C26H2705S2N  :S2.  12.89%  found  13.06%. 


21 

Para    Toluidine   Salt   of   Anthraquinone-l-Iso-Amyl-Thio-Ether-i- 

Sulfonic  Acid. 

1-C5H11S.C6H3  (CO)  2C6H3-8-S03HNH2C6H4CH3 

Orange  needles  which  melt  at  about  255 °C  with  de- 
composition. 

Substance  0.2005  g.  gave  0.1896  g.  BaSO4. 

Calculated  for  C26H2705S2N  :S2  12.88%  found  12.98%, 


22 

ANTHRAQUINONE-l-8-DI-THIO-ETHERS. 

Anthraquinone-l-8-Di-Methyl-Thio-Ether. 

1-CH3S.  C6H3(CO)2C6H3-8-SCH3. 

This  compound  was  obtained  as  a  by-product  in  the 
preparation  of  anthraquinone  l-methyl-thio-ether-8- 
sodium  sulfonate.  It  crystallized  from  benzene  in  lus- 
trous brownish  yellow  needles  which  melt  at  222 °C. 

Substance  0.2000  g.  gave  0.3075  g.     BaSO4. 

Calculated  for  C16H1202S2:S2.     21.35%  found  21.11%. 

Sulfone. 

1-CH3S02.C6H3  (CO)  2C6H3-8-S02CH3. 

Yellow  white  powder  which  melts  at  310 °C. 
Substance  0.2000  g.  gave  0.2527  g.    BaS04. 
Calculated  for  C16H1206S2:S2.     17.60%  found  17.35% 

Anthraquinone-l-Methyl-8-Ethyl-Di-Thio-Ether. 

1-CH3S.C6H3  (CO)  2C6H3-8-SC2H5. 

Gaseous  ethyl  mercaptan  was  passed  into  a  solution 
of  6  grams  of  anthraquinone-l-methyl-thio-ether-8-so- 
dium  sulfonate  in  300  cc.  of  water  and  1  gram  of  sodium 
hydroxide  for  3  hours.  Yield  3.5  grams  of  red  crystals 
which  melt  at  210°C. 

Substance  0.2009  g.  gave  0.2988  g.  BaS04. 

Calculated  for  C17H1402S2:S2.     20.40%  found  20.45%. 

Sulfone. 

1-CH3S02C6H3  (CO)  2C6H3-8-S02C2H5. 

Pale  yellow  crystalline  powder  which  melts  at  220  °C. 
Substance  0.2000  g.  gave  0.2446  g.  BaS04. 
Calculated  for  C17H1406S2:S2.     16.95%  found  16.79%. 


23 

Anthraquinone-l-Methyl-8-Propyl-Di-Thio-Ether. 

l-CH3S.C6H3(CO)2C6H3-8-SC3H7. 

6  grains  of  anthraquinone-l-methyl-thio-ether-8-so- 
dium  sulfonate  dissolved  in  300  cc.  of  water  and  1  gram 
of  sodium  hydroxide  were  refluxed  with  2  grams  of  80% 
propyl  mercaptan  for  three  hours.  Yield  5  grams  of 
orange  red  needles  which  melt  at  173. 5 °C. 

Substance  0.2000  g.  gave  0.2854  g.    BaS04. 

Calculated  for  C18H1602S2  :S2.     19.53%  found  19.60%. 

Sulfone. 

1-CH3S02.C6H3  (CO)  2C6H3-8-S02.C3H7. 


Yellow  white  powder  which  melts  at  211  °C. 
Substance  0.2000  g.  gave  0.2386  g.  BaS04. 
Calculated  for  C18H1606S2:S2.  16.34%  found  16 


.38%. 


Anthraquinone-l-Methyl-8-Butyl-Di-Thio-Etf 

1-CH3S.C6H3  (CO)  2C6H3-8-SC4H9. 

6  grams  of  anthraquinone-1-methy'  ,_thio_ether.8..So- 
dium  sulfonate  dissolved  in  250  cc.  of  water  and  j  m 
of  sodium  hydroxide  were  refluxed  w  lth  2  gramg  of  but  , 
mercaptan  for  three  hours.  Yie'ld  4  of 

needles  which  melt  at  134°C. 

Substance  0.2001  g.  gave  0^31  g     BaSO 
Calculated  for  C19H180,Sa:r^<     lg;73%  f()4und  1 

/       Sulfone. 

l-CH3S02.CeI58/cO)2CeH3-8-S02C4H, 
Light  yellow  pf>/wder  which  melts  at  169°C. 
Substance  0.^022  g.  gave  0.2266  g.    BaSO 
Calculated  'iOr  C19H1SO6S2:S2.     15.78%  found  15.38% 


24 


Anthraquinone-l-Methyl-8-Iso-Amyl-Di-Thio-Ether. 

1-CH3S.  C6H3(CO)2C6H3-8-SC5H11. 

7  grams  of  anthraquinone-l-methyl-thio-ether-8-so- 
dium  hydroxide  were  refluxed  with  2  grams  of  80%  iso 
amyl  mercaptan  for  three  hours.  Yield  3.5  grams  of  fine 
orange  needles  which  melt  at  114°C. 

Substance  0.2017  g.  gave  0.2661  g.  BaS04. 

Calculated  for  C20H2002S2  :S2.  17.99%  found  18.10%. 


Sulfone. 


i-CH3so2.c6H3  (CO) 


rown  powder  which  melts  at  172°C. 
SM>stance  0.2009  g.  gave  0.2208  g.  BaS04. 
Calculated  for  C20H20O6S2  :S2.  15.25%  found  15.09%, 


thraquinone  1-8-Di-Ethyl-Thio-Ether. 

l-C2H5S.CeB8  (CO)  2CeH3-8-SC2H5. 


This  compound  xwas  obtained  as  a  by-product  in  the 
preparation  of  a^thraquinone-l-ethyl-thio-ether-8-so- 
dium  sulfonate.  It  crystallizes  from  benzene  in  red 
crystals  which  melt  at  W7.5°C. 

Substance  0.2006  g.  gaV«  0.2842  g.  BaS04. 

Calculated  for  C18H16O2S2:S2.  19.53%  found  19.44%. 


Sulfone. 


1-C2H5S02C6H3  (CO)  2C6H3-8-S02C2H5. 

Pale  yellow  crystalline  powder  which  melts  at  228 °C. 
Substance  0.2000  g.  gave  0.2368  g.  BaSOv. 
Calculated  for  C18H1606S2  :S2.  16.35%  found  16.26%. 


25 


Anthraquinone-l-Ethyl-8-Butyl-Di-Thio-Ether. 


1-C2H5S.C6H3  (CO)  2C6H3-8-SC4H9. 

10  grams  of  anthraquinone-l-butyl-thio-ether-8-sodium 
sulfonate  suspended  in  50  cc.  of  water  and  1  gram  sodium 
hydroxide  were  refluxed  with  5  grams  ethyl  mercaptan 
for  three  hours.  Yield  three  grams  of  orange  yellow 
needles  which  melt  at  95 °C.  * 

Substance  0.2007  g.  gave  0.2664  g.BaS04. 

Calculated  for  C20H2002S2  :S2.  17.99%  found  18.14%. 


Sulfone. 

1-C2H5S02.C6H3  (CO)  2C6H3-8-S02C4H9. 

Yellow  white  crystalline  powder  which  melts  at  128 °C. 
Substance  0.2000  g.  gave  0.2249  g.  BaSO4. 
Calculated  for  C20H2006S2:S2.  15.25%  found  15.45%. 


Anthraquinone-l-8-Di-Propyl-Thio-Ether. 

1-C3H7S.C6H3  (CO)  2C6H3-8-SC3HT. 

This  compound  was  obtained  as  a  by-product  from  the 
preparation  of  anthraquinone  l-propyl-thio-ether-8-so- 
dium  sulfonate.  It  crystallizes  from  benzene  in  brick 
red  prisms  which  melts  at  142  °C. 

Substance  0.2003  g.  gave  0.2609  g.  BaS04. 

Calculated  for  C20H2002S2:S2.  17.99%  found  17.87%. 


Sulfone. 

1-C3H7S02.C6H3  (CO)  2C6H3-8-S02C3H7. 

Yellow  white  crystalline  powder  which  melts  at  21,0° C. 
Substance  0.2007  g.  gave  0.2159  g.  BaS04. 
Calculated  for  C20H20O6S2:S2.  15.25%  found  14.80%. 


26 

Anthraquinonc-l-Propyl-8-Butyl-Di-Thio-Ether. 

1-C3H7S.  C6H3  (CO)  2C6H3-8-SC4H9. 

5  grams  of  anthraquinone  l-butyl-thio-ether-8-sodium 
sulfonate  suspended  in  50  cc.  of  water  and  1  gram  of  so- 
dium hydroxide  were  refluxed  with  2.5  grams  of  80% 
propyl  mercaptan  for  six  hours.  Yield  5  grams  of 
orange  needles  which  melted  at  119.5° C. 

Substance  0.2000  g.  gave  0.2507  g.  BaS04. 

Calculated  for  C21H2202  S2  :S2.  17.31%  found  17.20%. 

Sulfone. 

1-C3H7S02.CCH8  (CO)  2C6H3-8-S02C4H9. 

Yellow  white  crystalline  powder  which  melts  at 
200.5°C. 

Substance  0.2000  g.  gave  0.2142  g.  BaS04. 
Calculated  for  C21H2206S2 :  S2.  14.76%  found  14.70%. 


Anthraquinone-l-Propyl-8-I*o-Amyl-Di-Thio-Ether. 

1-C3H7S.C6H3  (CO)  2C6H3-8-SC5H11. 

7  grams  of  anthraquinone  l-propyl-thio-ether-8-so- 
dium  sulfonate  dissolved  in  250  cc.  of  water  and  1  gram 
sodium  hydroxide  were  refluxed  with  2.5  grams  of  80% 
iso-amyl  mercaptan  for  four  hours.  Yield  4  grams  of 
orange  powder  which  melts  at  104 °C. 

Substance  0.2027  g.  gave  0.2444  g.  BaS04. 

Calculated  for  C22H2402S2:S2  16.68%  found  16.58%. 

Sulfone. 

1-C3H7S02C6H3  (CO)  2C6H3-8-S02C5H11. 

Brown  powder  melting  at  147.5 °C. 
Substance  0.2000  g.  gave  0.2034  g.  BaS04. 
Calculated  for  C22H2406S2 :  S2  14.30%  found  13.95%. 


27 

Anthraquinone-l-8-Di-Butyl-Thio-Ether. 

1-C4H9S.C6H3  (CO)  2C6H3-8-S.C4H9. 

This  compound  was  obtained  as  a  by-product  in  the 
preparation  of  anthraquinone  l-butyl-thio-ether-8-so- 
dium  sulfonate.  It  crystallizes  from  benzene  in  orange 
red  needles  which  melt  at  125 °C. 

Substance  0.2008  g.  gave  0.2382  g.  BaS04. 

Calculated  for  C22H24O2S2:S2  16.68%  found  16.28%. 

Sulfone. 

1-C4H9S02.C6H3  (CO)  2C6H3-8-S02C4H9. 

Pale  yellow  crystalline  powder  which  melts  at  138 °C. 
Substance  0.2000  g.  gave  0.2040  g.  BaS04. 
Calculated  for  C22H2406S2  :S2  14.30%  found  14.00%. 

Anthraquinone-l-Butyl-8-Iso-Butyl-Di-Thio-Ether. 

l-C4H9S.C6H3(CO)2C6H3-8-S  C4H9. 

7  grams  of  anthraquinone  l-butyl-thio-ether-8-sodium 
sulfonate  dissolved  in  250  cc.  of  water  and  1  gram  of  so- 
dium hydroxide  were  refluxed  with  2.5  grams  of  iso 
butyl  mercaptan  for  3  hours.  Yield  4  grams  of  orange 
colored  prisms  which  melt  at  103.5°C. 

Substance  0.2000  g.  gave  0.2429  g.  BaSO4. 

Calculated  for  C22H24O2S2:S2  16.68%  found  16.70%. 


Sulfone. 

1-C4H9S02.C6H3  (CO)  2C6H3-8-S02C4H9. 

Light    yellow    crystalline    powder    which    melts    at 
168.5°C. 

Substance  0.2000  g.  gave  0.2034  g.  BaS04. 
Calculated  for  C22H24O6S2  :S2  14.30%  found  13.95%. 


28 

Anthraquinone-l-Butyl-8-Iso-Amyl-Di-Thio-Ether. 

1-C4H9S.C6H3  (CO)  2C6H3-8-SC5H11. 

7  grams  of  anthraquinone-l-butyl-thio-ether-8-sodium 
sulfonate  dissolved  in  300  cc.  of  water  and  1  gram  of  so- 
dium hydroxide  were  refluxed  with  2  grams  of  iso-amyl 
mercaptar*  f  or  three  hours.  Yield  4  grams  of  orange 
crystals  which  melt  at  116.5°C. 

Substance  0.2004  g.  gave  0.2366  g.  BaS04. 

Calculated  for  C23H2602S2:S2  16.09%  found  16.21%. 

Sulfone. 

1-C4H9S02.C6H3  (CO)  2C6H3-8-S02C5H11. 

Pale  yellow  powder  which  melts  at  154° C. 
Substance  0.2023  g.  gave  0.2055  g.  BaSO4. 
Calculated  for  C23H26O6S2  :S2  13.87%  found  13.94%. 


Anthraquinone-l-8-Di-Iso-Amyl-Thio-Ether. 

l-CAACeH.  (CO)  AH.-8-SC.H,,. 

.  This  compound  was  obtained  as  a  by-product  in  the 
preparation  of  anthraquinone  l.-iso-amyl-thio-ether-8-so- 
dium  sulfonate.  It  crystallizes  from  benezene  in  orange 
red  elongated  plates  which  melt  at  133 °C. 

Substance  0.2004  g.  gave  0.2226  g.  BaS04. 

Calculated  for  C24H2S02S2:S2  15.55%  found  1*.27%. 

Sulfone. 

l-C5H11S01.C9H,(CO)aC6H.-8-SOaCaH11 

Yellow  needles  which  melt  at  176°C. 
Substance  0.2000  g.  gave  0.1952  g.  BaSO4. 
Calculated  for  C24H2806S2 :S2  13.46%  found  13.40%. 


29 


BIOGRAPHY. 

George  Edgar  Miller  was  born  in  Abbottstown,  Penn- 
sylvania, November  13,  1891.  His  early  education  was 
received  in  the  public  schools  of  that  place.  In  1905  he 
removed  to  Gettysburg  where  he  finished  his  grammar 
school  work  and  was  graduated  from  High  School  in 
1910.  The  same  year  he  entered  Gettysburg  College 
and  was  awarded  the  degree  of  Bachelor  of  Science  in 
1914.  The  years  1914-1916  were  spent  at  the  Univer- 
sity of  Pennsylvania  in  graduate  work  in  Chemistry. 
The  next  year,  1916-17  he  attended  the  Johns  Hopkins 
University  taking  Chemistry  as  his  major,  and  Physical 
Chemistry  and  Mineralogy  as  his  minor  subjects.  The 
next  two  years  he  spent  with  E.  I.  du  Pont  de  Nemours 
&  Company  at  Wilmington,  Delaware.  The  year  1919- 
20  he  was  again  in  attendance,  in  the  graduate  chemistry 
department,  of  the  Johns  Hopkins  University. 


Syracuse,  N.  Y. 
PAT.  JAN.  21.  1908 


461991 


UNIVERSITY  OF  CALIFORNIA  LIBRARY 


